US20210087320A1 - Styrene Maleamide Block Copolymer Pigment Dispersant - Google Patents

Styrene Maleamide Block Copolymer Pigment Dispersant Download PDF

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US20210087320A1
US20210087320A1 US16/954,867 US201816954867A US2021087320A1 US 20210087320 A1 US20210087320 A1 US 20210087320A1 US 201816954867 A US201816954867 A US 201816954867A US 2021087320 A1 US2021087320 A1 US 2021087320A1
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meth
group
polymeric dispersant
acrylate
mole
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Andrew J Shooter
Robert A. Jennings
Sebastien Perrier
Majda Akrach
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University of Warwick
Lubrizol Advanced Materials Inc
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University of Warwick
Lubrizol Advanced Materials Inc
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Assigned to LUBRIZOL ADVANCED MATERIALS, INC. reassignment LUBRIZOL ADVANCED MATERIALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JENNINGS, Robert A, SHOOTER, Andrew J
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • B01F17/0057—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/22—Amides or hydrazides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to a polymeric dispersant from controlled radical polymerization of soluble (meth)acrylate or (meth)acrylamide blocks with styrene-maleic anhydride blocks.
  • the anhydride groups of the styrene-maleic anhydride may be reacted with dialkylamino alkyl amines or aminoalkyl substituted nitrogen containing aromatic and/or heterocycles to form pendant tertiary amine type groups that can provide enhanced anchoring to a variety of pigments or particulate filler materials.
  • the polymers may be diblock or up to ten alternating blocks.
  • Dispersants for pigments and other particulates are known. Dispersants generally have an anchoring portion of the molecule that has some attraction for and anchors to the pigment or particulate surfaces and a solubilizing portion that interacts favorably with the continuous phase. When the solubilizing portion is anchored to the pigment or particulate, the solubilizing portion acts as a barrier to aggregation of the particulate.
  • U.S. Pat. No. 9,416,280 (WO2008/122606) relates to a dispersant from a copolymer of a monomer (A) and a monomer (B) often B is maleic anhydride.
  • the anhydride group is reacted with (i) a compound containing at least one tertiary or heterocyclic amine site and at least one additional groups capable of reacting with the dicarboxylic acid or anhydride thereof, and (ii) a polyetheramine.
  • U.S. Pat. No. 7,838,574 relates to a pigment dispersion with a copolymer dispersant having a hydrophobic block (A) and a hydrophilic block (B).
  • U.S. Pat. No. 8,153,731 (DE102006062439) relates to comb polymers made by reacting styrene-maleic anhydride copolymer with primary amino-terminated polyalkylene oxide used as a wetting agent and/or dispersant.
  • U.S. Pat. No. 8,129,476 (DE102006062441 relates to similar comb polymers where the maleic anhydride units are derivatized with phosphate or quaternary ammonium functions.
  • U.S. Pat. No. 4,755,563 relates to block copolymer dispersants containing ionic moieties.
  • the block copolymers are preferably made by group transfer polymerization techniques and can be used as pigment dispersants.
  • Controlled radical polymerization of block copolymer dispersant where the solvent solubilizing block(s) is typically (meth)acrylate and/or (meth)acrylamide repeat units and the anchoring block(s) and is typically styrene-maleic anhydride are useful to form dispersions of particulates in a nonpolar or polar organic medium. It is desirable if each block of solubilizing repeat units or anchoring repeat units is at least 5 and more desirably at least 10 consecutive units to enhance the surface activity of the final dispersant.
  • Controlled free radical polymerization is useful to make such consecutive blocks of organic media soluble (such as acrylate type) repeating units and copolymer blocks of styrene type repeat units and free radically polymerizable di or tricarboxylic acid monomers (such as maleic anhydride type) repeat units.
  • Maleic anhydride likes to copolymerize in alternating steps with styrene free radically. So, the anchoring block typically has at least one styrene repeat unit between each maleic anhydride repeat unit.
  • a portion or all of the dicarboxylic acid repeating units are converted to having amide or imide linkages by reacting with an aminic species (having an amine group reactive with carboxylic acid to form an amide or imide linkage and at least one second amine group that is characterized as a tertiary amine or a cyclic amine containing structure (optionally with aromaticity) to form the final dispersant.
  • an aminic species having an amine group reactive with carboxylic acid to form an amide or imide linkage and at least one second amine group that is characterized as a tertiary amine or a cyclic amine containing structure (optionally with aromaticity) to form the final dispersant.
  • the dicarboxylic acid (or anhydride thereof) groups of the styrene-maleic anhydride type segment may be reacted with dialkylamino alkyl amines and similar species (containing polyamines, imidazoles, pyrrolidine, morpholine, pyridine, piperidine, piperazine, pipecoline) containing at least one reactive primary amine and a tertiary amine or heterocyclic with an amine group(s) that can provide enhanced anchoring to a variety of pigments or particulate filler materials.
  • the polymers may be diblock or up to 10 alternating blocks of solubilizing chains and anchoring chains.
  • solubilizing chains not contain any significant amount of highly polar species such as (meth)acrylic acid repeat units. It is desirable that the anchoring block not contain highly polar groups or groups greater than 3 units of polyethylene oxide.
  • Block copolymers based on butylacrylate-co-styrene maleic anhydride post modified with dimethylamino propyl amine were found to be excellent pigment dispersants as fluid millbases and low pigment particle size distributions were achieved for the dispersion of Pigment Red 254.
  • Low particle size dispersions are desirable for highly transparent coatings such as those used in colour filters, also known as LCD (liquid crystal displays), or automotive tinted clear coats.
  • a polar or nonpolar solvent-based composition comprising a particulate solid, an organic solvent and a polymeric dispersant wherein:
  • solubilizing block or the anchoring block can occur first and optionally there is one additional solubilizing or one additional anchoring block but such that the total number of solubilizing blocks does not exceed the maximum value of v and the total number of anchoring blocks does not exceed the maximum value of v (such as 5, 3, or 2 depending on the range of v);
  • solubilizing block is -(A) x - and the anchoring block is a copolymer of the structure — ⁇ (B) y -(D) z ⁇ u —;
  • x is at least 5; and desirably 5 to 150, and more preferably 5 to 100;
  • y is at least 1 and can be from 1 to 10, more desirably 1 to 5;
  • z is generally 1 when derived from polymerizing maleic anhydride but can be 2, 3, 4 or 5, especially when derived by other dicarboxylic acids or anhydrides such as itaconic acid;
  • u is 1 to 25, preferably 2 to 10 or 2 to 20, more preferably 3 to 10 or 3 to 20;
  • u(y+z) is at least 5, desirably from 5 to 100, more preferably 5 to 50;
  • v is 1 to 5, preferably 1 to 3 and more preferably 1 to 2;
  • repeating units of the A structure comprises about 25 to 80 wt. % of the dispersant
  • repeating units of the B structure comprises from about 5 to about 35 wt. % of the dispersant
  • combined repeating units of the D structure are from about 5 to about 50 wt. % of the dispersant
  • said dispersant has a number average molecular weight at least 2500 daltons, preferably less than 75000 daltons, and more preferably 5000 to 20000 daltons.
  • At least 90, 95, 99 or 100 mole % of the A units are selected from the group consisting of A 1 , A 2 , A 3 , A 4 , A 5 and A 6 units, at least 80, 90, 95 or 98 mole % of the A repeat units in the block copolymer dispersant are selected from the groups consisting of A 1 , A 2 , and A 3 and the remainder of the A groups (such as 20 mole % or less, 10 mole % or less, 5 mole % or less and 2 mole % or less) are selected from A 4 , A 5 , or A 6 .
  • At least 80, 90 or 95 mole % of A is selected from A 1 and the remaining amounts of A are selected from the other units A 2 and or A 3 in amounts of 20 mole % or less, 10 mole % or less and 5 mole % or less and, A 4 , A 5 and A 6 in the amounts of 20 mole % or less, 10 mole % or less, and 5 mole % or less, and 2 or 1 mole % or less based on the total amount of A repeating units in the block copolymer dispersant.
  • a 4 is similar to a repeat unit in the anchoring segment of the block copolymer dispersant, we don't want too many A 4 repeat units in the solubilizing portion of the block copolymer dispersant. Since A 5 and A 6 can have high molecular weights, even a small molar amount of A 5 or A 6 can add significant weight amounts of polar polymers to the block copolymer and thus these repeat units are also used in relatively low molar amounts.
  • a 1 is as defined below one or more repeating units derived from an alkyl(meth)acrylate of 4 to 24 carbon atoms, preferably a repeat unit of the structure
  • R 1 is CH 3 or H
  • R 2 is a linear or branched C 1-20 alkyl group more desirably C 1 -C 16 alkyl group, (optionally including 1 or 2 heteroatoms such oxygen (resulting occasionally in a hydroxyl group or ether linkage or nitrogen)) wherein * indicates a covalent bond to the next/adjacent repeating units in the polymer or a covalent bond to the rest of a shown molecule
  • a 1 is a repeat unit from radically polymerizing an alkyl(meth)acrylate or mixture of alkyl(meth)acrylates, preferably alkyl acrylate and more preferably butyl acrylate.
  • the (meth) means that a methyl group is optionally present.
  • Typical alkyl (meth)acrylates that can be used as a co-monomer include C 1-20 or desirably C 1 -C 16 alkyl polymerisable ethylenically unsaturated monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate.
  • Typical (meth)acrylates with heteroatoms that can be used as a comonomer include hydroxyethyl (meth)acrylate (e.g., HEMA), hydroxy butyl (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, diethylene glycol ethyl ether (meth)acrylate, and di(ethylene glycol) 2-ethylhexyl ether (meth)acrylate.
  • a 2 is derived from polymerizing one or more repeating units disubstituted (meth)acrylamide monomers and is according to the formula below
  • R 1 is as defined above and R 9 and R 10 individually are C 1 -C 8 alkyl or aromatic or combinations of alkyl and aromatic groups or combinations thereof, optionally with a hydroxyl group, and optionally R 9 and R 10 can be connected to each other to form C 2 -C 16 cyclic groups, wherein the R 9 and R 10 groups are selected from an alkyl, alkanol or aromatic for example (meth)acrylamide, N-ethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N′N-dimethyl (meth)acrylamide, N′N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-(isobutoxymethyl) methacrylamide, 3-(methoxypropyl)(meth)acrylamide, N-tertbutyl (meth)acrylamide, N-phenyl(meth)acrylamide, and N-diphenylmethyl (
  • a 3 may be one or more repeat units from radically polymerizing an aromatic monomer of the structure
  • R 11 is an C 6 -C 12 aromatic or combination of aromatic and alkyl group optionally including hydroxyl group(s) and alkylene oxide group(s) substituted with an alkyl group for example an aromatic (meth)acrylate or mixtures of aromatic (meth)acrylates.
  • Typical aromatic (meth)acrylates that can be used as co-monomer include, phenoxyethyl (meth)acrylate, ethylene glycol phenyl ether (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and benzyl (meth)acrylate.
  • benzyl (meth)acrylate is the A 3 repeat unit.
  • a 4 is a repeat unit from radically polymerizing one or more aromatic vinyl monomer and would have the structure as shown below
  • R 1 is H or methyl and R 3 is one or more halogens, C 1 -C 10 alkyl and/or aromatic group and preferably H or a C 1 to C 4 alkyl group, optionally including a halogen, one or more oxygen atom, and optionally including a nitrogen atom such as nitro group.
  • the variable e can be 1, 2, 3, 4 or 5.
  • at least 80 mole % of the R 3 is preferably H.
  • desirably 10 mole % or less, more desirably 5 mole % or less, and preferably 2 mole % or less of A units can be repeat units from an aromatic vinyl monomer such as A 4 .
  • a 4 can be a repeat unit from radically polymerizing styrene or substituted styrene for example from polymerizing 4-acetoxystyrene, 4-benzhydrylstyrene, 4-benzyloxy-3-methoxystyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 4-tert-butoxystyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,6-dichlorostyrene, 2,6-difluorostyrene, 3,4-dimethoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, N,N-dimethylvinylbenzylamine, 4-ethoxystyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 4-[N
  • a 5 is a repeat unit from radically polymerizing one or more polyester (meth)acrylate monomer of the formula
  • —O—R 12 is at least one polymer chain comprising of a polyester with a number average molecular weight of at least 200. More desirably the number average molecular weight of each polyester segment (R 12 ) on A 5 is in the number average molecular weight range of 300 to 5000, or 500 to 3000, or 1000 to 2500 dalton.
  • An example of a monomer comprising a polyester chain is hydroxyethylcaprolactone acrylate (HELCA)
  • the —O—R 12 portion of the A 5 repeat unit from radically polymerizing a monomer comprises of a polyester chain derived from polymerizing a lactone, dioxane-2,5-dione or a hydroxycarboxylic acid, or mixtures thereof.
  • lactones include ⁇ -propiolactone and optionally C 1-6 -alkyl substituted ⁇ -valerolactone and ⁇ -caprolactone such as ⁇ -methyl- ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, 2-methyl- ⁇ -caprolactone, 3-methyl-8-caprolactone, 4-methyl-8-caprolactone, 5-tert butyl-8-caprolactone, 7-methyl- ⁇ -caprolactone, 4,4,6- ⁇ -caprolactone trimethyl- ⁇ -caprolactone 4,6,6-trimethyl- ⁇ -caprolactone, or mixtures thereof.
  • suitable dioxane-2,5-diones include lactide or glycolide.
  • A is a monomer that contains at least one polyester chain derivable from ⁇ -valerolactone and ⁇ -caprolactone.
  • the —O—R portion of A 5 is derived from polymerizing hydroxy carboxylic acid that may be saturated or unsaturated, linear or branched.
  • suitable hydroxy carboxylic acids are glycolic acid, lactic acid, 5-hydroxy valeric acid, 6-hydroxy caproic acid, ricinoleic acid, 12-hydroxy stearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid 4-hydroxydecanoic acid, or mixtures thereof.
  • the polyester made by condensation reactions may be esterification products prepared by the reaction of one or more organic polycarboxylic acids or their anhydrides (e.g., of molecular weight less than 300 and more preferably less than 150 dalton) with one or more low molecular weight (e.g., less than 250 and more desirably less than 150 dalton) diol.
  • suitable polyols for use in the reaction include polyglycol adipates, polyethylene terephthalate polyols, orthophthalic polyols and the like, and mixtures thereof.
  • the diols used in making the polyester can be aliphatic, cycloaliphatic or aromatic and include alkylene glycols, e.g., ethylene glycol, 1,2- and 1,3-propylene glycols, 1,2-, 1,3-, 1,4- and 2,3-butylene glycols, hexane diols, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol and other glycols such as bisphenol-A, cyclohexane diol, cyclohexane dimethanol (1,4-bis-hydroxymethylcycohexane), 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl prorane-1,3-diol, VersaticTM alcohols produced from CARDURA E10P (Hexion), triethylene glycol, te
  • Suitable carboxylic acids used in making the polyester include dicarboxylic acids and tricarboxylic acids and anhydrides, e.g., maleic acid, maleic anhydride, succinic acid, glutaric acid, glutaric anhydride, adipic acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, chlorendic acid, 1,2,4-butane-tricarboxylic acid, phthalic acid, the isomers of phthalic acid, phthalic anhydride, fumaric acid, tetrabromophthalic anhydride and acid, dimeric fatty acids such as oleic acid, and the like, and mixtures thereof.
  • Preferred polycarboxylic acids used in making the polyester polyols include aliphatic or aromatic dibasic acids.
  • a 6 is a repeat unit from radically polymerizing a polyalkylene oxide (meth)acrylate (such as poly(ethylene glycol) (meth)acrylate) or a mixture of polyalkylene oxide (meth)acrylates of the formulae below
  • R 1 is selected from H or methyl and R 13 is a polyalkylene oxide, preferably having a number average molecular weight of 200-3000 dalton or poly(propylene glycol) (meth)acrylate having number average molecular weight of 200 to 3000.
  • B is a repeat unit from radically polymerizing an aromatic vinyl monomer and would have a structure such as shown below
  • R 1 is H or methyl and R 3 is one or more halogens or C 1 -C 10 alkyl and/or aromatic group and preferably H or a C 1 to C 4 alkyl group, optionally including a halogen, one or more oxygen atom, and optionally including a nitrogen atom such as nitro group.
  • the variable e can be 1, 2, 3, 4 or 5. In one embodiment, at least 80 mole % of the R 3 is preferably H.
  • B is a repeat unit from radically polymerizing styrene or substituted styrene.
  • styrene or substituted styrene.
  • D′ is an example of a repeat unit from maleic anhydride monomer reacted with an aminic dialkylaminoalkylarnine, a substituted dialkylaminoalkylanine, or an aminoalkyl substituted nitrogen containing aromatic heterocycle or mixtures thereof desirably having 4 to 6 carbon atoms, preferably D′ 3 (amide form) or D′ 4 (imide form) repeat units.
  • D′′ is an example of a repeat unit from an itaconic acid monomer reacted with an aminic dialkylaminoalkylamine, a substituted dialkylaminoalkylamine, or an aminoalkyl substituted nitrogen containing aromatic heterocycle or mixtures thereof desirably having 4 to 6 carbon atoms, preferably D′′ 3 (amide form) or D′′ 4 (imide form) repeat units.
  • Examples of a dialkylaminoalkylarmine include dimethylarminoethylamine, diethylaminopropylamine, or dimethylaminopropylamine.
  • Examples of a suitable imidazole include 1-(3-aminopropyl)imidazole, 1-(3-aminobutyl)imidazole, 1-(3-aminopentyl)imidazole, l-(3-aminohexyl)imidazole, 1-(3-aminoheptyl)imidazole, 1-(3-aminooctyl)imidazole, or mixtures thereof.
  • Examples of suitable amino alkyl pyridines include 2-(2-aminoethyl)pyridine, 3-(2-aminoethyl)pyridine, 4-(2-aminoethyl)pyridine.
  • Examples of pyridines include 2-(2-pyridyl)ethylamine, 4-(2-aminoethyl)pyridine, 4-(1-aminoethyl)pyridine, 3-(2-aminoethyl)pyridine, 2-(1-aminoethyl)pyridine, and 1-pyridin-3-yl-ethylamine, 2-(2-methylaminoethyl)pyridine, 4-(aminomethyl)pyridine, 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-3-methylpyridine, 2-amino-3-methylpyridine, 4-amino-2-methylpyridine, 5-amino-2-methylpyridine, 3-amino-4-methylpyridine, 3-amino-5-methyl
  • a non-tertiary nitrogen containing amine may be present.
  • amines that can be reacted with the dicarboxylic acid of the anchoring chain in lieu of the amines with tertiary nitrogen, aromatic nitrogen, heterocycle nitrogen, or imidazole; include alkyl amines with C 1 -C 20 carbon atoms for example methyl, propyl, butyl, pentyl, hexyl amine or aromatic amines for example phenyl amine and phenyl ethyl amine.
  • less than 30 mole %, more desirably less than 20 mole %, preferably less than 10 or in some embodiments less than 5 or 1 mole percent of the total D units of the block copolymer dispersant that have amide or imide linkages to the aminic reactant would comprise amines that do not have a tertiary amine, an aromatic amine with a nitrogen in the aromatic ring, or an imidazole.
  • the complementary amount (to make 100%) of the D units would be the dicarboxylic acid repeat units, the anhydride of the D unit, or the amide and imide form of the D units.
  • D is comprised of D 1 , D 2 , D 3 and D 4 and desirably D 1 , D 2 , D 3 and D 4 comprise at least 90, 95, 98, 99 or 100 mole % of D.
  • D′ 3 (amide form), and D′ 4 (imide form) or D′′ 3 (amide form), and D′′ 4 (imide form) are examples of how repeat units from dicarboxylic acid monomer, D′ 1 (maleic anhydride) or D′′ 1 (itaconic acid) react with amines.
  • D, or examples D′ 1 or D′′ 1 are optionally reacted with an aminic reactant that contains at least 1 and maybe up to 2, 3 or 4 nitrogen (amines) at least one of which is not reactive with carboxylic acid groups such as 1) tertiary amines or 2) amines where the nitrogen atom is part of a cyclic or heterocyclic ring, or 3) amines where the nitrogen is part of an aromatic ring or is bound to one carbon atom by a single bond and another carbon atom by a double bond (aromatic rings with amine therein and imidazoles).
  • Tertiary amines are amines where the nitrogen is attached to at least three different aliphatic carbon atom groups.
  • the aminic reactant desirably has at least 2 and up to 10, more desirably at least 2 and up to 6 or 8, and preferably at least 2 and up to 4 nitrogen atoms.
  • the aminic reactant desirably has 4 to 30 carbon atoms, more desirably 4 to 20 carbon atoms and preferably 4 to 10 or 15 carbon atoms (optionally including one or two oxygen atoms).
  • the aminic reactant reacts to the dicarboxylic acid or anhydride through a primary or secondary amine to form an amide or imide linkage as shown in D′ 3 and D′′ 3 (amide form) or D′ 4 and D′′ 5 (imide form).
  • up to 10 or 20 mole % of the aminic reactant can have multiple primary or secondary amine groups such that it can couple two different block copolymer dispersants into a larger dispersant.
  • less than 10 mole % or less than 5 mole % or less than 2 mole % of the aminic reactant can have more than one amine group capable of forming an amide or imide bond with a dicarboxylic acid or anhydride thereof.
  • the following structures show some of the potential derivatives of the aminic reactant and either maleic anhydride derived repeat units or itaconic acid derived repeat units in the block copolymer dispersant.
  • At least 80 mole % of the D units are reacted with an aminic reactant to form an amide or imide that contains a tertiary amine. In one embodiment, at least 80 mole % of the D units are reacted with an aminic reactant to form an amide or imide that contains an amine where the nitrogen is part of an aromatic ring or part of an imidazole ring. In one embodiment, at least 80 mole % of the D units are reacted with an aminic reactant to form an amide or imide that contains at least one of the group consisting of a tertiary amine, a nitrogen as part of an imidazole, and a nitrogen as part of an aromatic ring.
  • a polyamine may be present such that 1-10% of the dicarboxylic groups are reacted and it is anticipated that these will induce some intermolecular crosslinking.
  • examples of poly(amines) are ethylenediamine, diethylene triamine.
  • Polyamines may contain secondary or tertiary amines for example tetraethylene pentamine or trimethyldiethylenetriamine.
  • the compound containing at least one tertiary or heterocyclic amine may be a dialkylaminoalkylamine, a substituted dialkylaminoalkylamine, an aminoalkyl substituted nitrogen containing aromatic heterocycle, a dialkylaminoalkyl alcohol, a hydroxyalkyl substituted nitrogen containing aromatic heterocycle, or mixtures thereof.
  • the compound containing at least one tertiary or heterocyclic amine may be a dialkylaminoalkylamine, a substituted dialkylaminoalkylamine, or mixtures thereof.
  • the dialkylaminoalkylamine may be represented by the formula R 2 (R 3 )NR 4 NH 2 wherein R 2 and R 3 are independently C 1 -C 6 alkyl moieties. R 2 and R 3 may be taken together to form a cyclic structure containing 5 to 8 carbon atoms. R 4 includes C 1 to C 12 linear or branched alkylene.
  • dialkylaminoalkylamine examples include dimethylaminoethylamine, diethylaminopropylamine, or dimethylaminopropylamine.
  • the substituted dialkylaminoalkylamine may be represented by the formula R 2 (R 3 )NR 4 NR 5 , wherein R 2 , R 3 and R 4 are defined above, and R 5 is H or an optionally substituted linear or branched hydrocarbyl group.
  • the dialkanolaminoalkyl amine may be represented by the formula HO—R 2 (HO—R 3 )NR 4 NR 5 , wherein R 2 , R 3 and R 4 are defined previously.
  • suitable dialkanolaminoalkyl amine includes N,N-bis(2-hydroxyethyl)ethylenediamine and [2-aminoethyl(hydroxymethyl)amino]methanol.
  • aminoalkyl substituted nitrogen containing aromatic, heterocycle, or imidazole may include groups such as an imidazole, a pyridine a triazole, a pyrazole, a tetrazole, or mixtures thereof.
  • aminoalkyl substituted nitrogen containing aromatic heterocycle includes an imidazole, optionally substituted with C 1-4 groups.
  • Examples of a suitable imidazole include 1-(3-aminopropyl)imidazole, 1-(3-aminobutyl)imidazole, 1-(3-aminopentyl)imidazole, 1-(3-aminohexyl)imidazole, 1-(3-aminoheptyl)imidazole, 1-(3-aminooctyl)imidazole, or mixtures thereof.
  • aminoalkyl substituted nitrogen is an imidazole.
  • Examples of a suitable imidazole include examples include 2-aminoimidazole, 2-aminobenzimidazole, 1-(3-aminopropyl)imidazole, 1-(3-aminopropyl)-2-methyl-1H-imidazole, 2-(1H-imidazol-1-yl)ethanamine, 2-(2-methyl-1H-imidazol-1-yl)ethylamine, or mixtures thereof.
  • Another aminic reactant can include V-phenyl-p-phenylenediamine.
  • the tertiary amine group of the dialkylaminoalkylamine, or the other nitrogen(s) attached with three covalent bonds to non-carbonyl carbon atoms may be quaternised.
  • Quaternising agents include alkyl halides, aralkyl halides, dialkyl carbonates, dialkyl sulphates or epoxides.
  • Particularly useful quaternising agents for the graft copolymer of Formula (1) include benzyl chloride, dimethyl sulphate, diethyl sulphate propylene oxide, or styrene oxide. Often epoxides are used in the presence of equal molar quantity of acid (such as acetic acid).
  • the degree of quaternising may be from greater than 1%, or greater than 10%, or greater than 20% and or 40% or more of the amine moieties.
  • the degree of quaternising may be as high as 100%, or 95% or 90% of the amine moieties. In different embodiments, the degree of quaternising ranges from greater than 1% to 100%, or greater than 10% to 95%, or greater than 20% to 95%, or 40% to 90%.
  • the dispersant of the invention may be obtained by a process comprising 1) synthesis of a block copolymer and 2) reaction of block copolymer with dialkylaminoalkylamine, a substituted dialkylaminoalkylamine, an aminoalkyl substituted nitrogen containing aromatic, heterocycle, or imidazole.
  • the styrene maleic anhydride copolymer could be generated, the maleic anhydride based repeating unit could be functionalized with the aminic reactant, and then one or more solubilizing blocks could be added to the styrene-maleic anhydride block.
  • the block copolymer may be synthesised from any living or controlled polymerization technique especially control radical polymerisation (CRP) processes. e.g., cobalt catalysed chain transfer polymerisation, nitroxide mediated polymerisation, atom transfer radical polymerisation, iodine transfer polymerisation, selenium-centered radical-mediated polymerisation, telluride mediated polymerisation, stilbene-mediated polymerisation, organocatalyzed living radical polymerisation, and preferably reversible addition fragmentation chain transfer (RAFT) polymerisation.
  • CRP control radical polymerisation
  • cobalt catalysed chain transfer polymerisation e.g., cobalt catalysed chain transfer polymerisation, nitroxide mediated polymerisation, atom transfer radical polymerisation, iodine transfer polymerisation, selenium-centered radical-mediated polymerisation, telluride mediated polymerisation, stilbene-mediated polymerisation, organocatalyzed living radical polymerisation,
  • a suitable solvent may be chosen from aromatic hydrocarbons, such as toluene and xylene, aliphatic hydrocarbons, alkyl esters of alkane carboxylic acids, dialkyl ketones and dialkyl and cyclic ethers such as diethyl ether and tetrahydrofuran.
  • suitable solvents include alkyl esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, methyl propionate, methoxy propyl acetate, ethyl butyrate, or mixtures thereof.
  • the process to prepare the polymer of the invention may have a reaction temperature in the range ⁇ 80 to 250° C., or 20 to 220° C. or 40 to 200° C.
  • the choice of solvent and initiator will may or may not have a limiting or non-limiting effect on the preferred polymerisation temperature range.
  • OLRP organocatalysed living radical polymerization
  • ester solvent An organocatalysed living radical polymerization (OLRP) process performed in ester solvent is preferred.
  • OLRP polymerization are carried typically performed utilizing an alkyl iodide initiator in the presence of an organic catalyst as described in US 2012/190795, U.S. Pat. No. 8,575,285B2, U.S. Pat. No. 9,018,325B2 and U.S. Pat. No. 8,742,045B2.
  • examples of initiators for OLRP are ethyl ⁇ -iodophenylacetate, 2-iodo-2-methylpropionitrile, ethyl 2-iodo-2-methylpropionate, ethyl 2-iodopropionate.
  • the initiator may be synthesised in situ by reacting iodine with a free radical initiator for example 2,2′-azobis(2,4-dimethylvaleronitrile) (V65) or 2,2′-azobis(isobutyronitrile) (V60).
  • a free radical initiator for example 2,2′-azobis(2,4-dimethylvaleronitrile) (V65) or 2,2′-azobis(isobutyronitrile) (V60).
  • catalysts for OLRP are tributyl amine, tetra butyl ammonium iodide, N-iodosuccinimide, diethyl phosphonate, diphenylmethane, 2,6-Di-tert-butyl-4-methylphenol and Vitamin E compounds.
  • a RAFT polymerisation process performed in an ester solvent is especially preferred.
  • RAFT polymerisations are carried out utilising thiocarbonylthio chain transfer agents, e.g., cyanomethyl methyl(phenyl)carbamodithioate, cyanomethyl dodecyl trithiocarbonate, 2-cyano-2-propyl benzodithioate, 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, 2-cyano-2-propyl dodecyl trithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, or 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid.
  • thiocarbonylthio chain transfer agents e.g., cyanomethyl methyl(phenyl)carbamodithioate, cyanomethyl dodec
  • a free radical initiator in the presence of RAFT agent or OLRP catalyst to accelerate the polymerization.
  • the initiator may be an oil soluble azo or peroxide type initiator.
  • Azo initiators and related Wako product codes are dimethyl 2,2′-azobis(2-methylpropionate) (V601), 2,2′-azobis(2,4-dimethylvaleronitrile) (V65), 2,2′-azobis(isobutyronitrile) (V60), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V70), 2,2′-azobis(2-methylbutyronitrile) (V59), or 1,1′-azobis(cyclohexanecarbonitrile) (V40).
  • peroxide initiators are dilauroyl peroxide, dibenzoyl peroxide, t-butyl perbenzoate, t-butyl peroxyacetate, t-butyl peroxy-2-ethylhexanoate (Trigonox® 21S ex Akzo Nobel).
  • the living polymerization is conducted sequentially (in any order of solubilizing and anchoring) once with the solubilizing monomer(s) and one with the anchoring monomers. If a tetrablock copolymer dispersant is desired, the living polymerization is conducted sequentially four times. As the polymerization can switch from solubilizing monomer(s) to anchoring monomers or vice versa, the order of polymerization of the monomers is not critical.
  • monomer component forming A e.g., alkyl (meth)acrylate
  • free radical initiator and RAFT agent or OLRP initiator and catalyst are stirred in solvent under nitrogen at 60-100° C. for 2-24 hours until all the monomer has converted to polymer.
  • monomer conversion of component A is greater than 95% to enhance blocking efficiency.
  • Monomer components B and D are then charged and stirred under nitrogen for 60-100° C. for 2-24 hours until all the monomer has converted to polymer. Additional initiators may be added at any time to increase reaction rate.
  • the final polymer can be stirred under nitrogen with an aminic reactant comprising a dialkylaminoalkylamine, a substituted dialkylaminoalkylamine, or an aminoalkyl substituted nitrogen containing aromatic heterocycle, or imidazole at temperatures from 0-300° C., preferably 25 to 200° C. and especially 80-180° C.
  • a reaction temperature of less than 100° C. will typically favour formation of amides.
  • a reaction temperature of 150° C. or greater will typically favour formation of imides if the amine reactant is a primary amine.
  • the resultant copolymer may contain a mixture amide or imide groups and smaller amounts of dicarboxylic acid and or anhydride.
  • the RAFT agent may be cleaved from the polymer chain end.
  • the resulting product may remain in the reaction solvent or be removed by a separation technique.
  • An example of removing the cleaved RAFT agent from the polymer solution may be to filter through an ion exchange resin/activated carbon or separate the polymer from solution by precipitation.
  • Suitable solvent may be chosen from aromatic hydrocarbons, such as toluene and xylene, aliphatic hydrocarbons, alkyl esters of alkane carboxylic acids, dialkyl ketones and dialkyl and cyclic ethers such as diethyl ether and tetrahydrofuran.
  • suitable solvents include alkyl esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, methyl propionate, methoxy propyl acetate, ethyl butyrate, or mixtures thereof.
  • any quaternization of tertiary or other nitrogen atoms bound to aliphatic or aromatic carbons by three covalent bonds can be implemented.
  • the reaction conditions for quaternization are well known to those skilled in the art.
  • the RAFT agent maybe removed before the addition of the dialkylaminoalkylamine, substituted dialkylaminoalkylamine, or aminoalkyl substituted nitrogen containing aromatic heterocycle. Examples of processes for removal of the RAFT agent are described in Polym. Chem., 2010, 1, 149-157.
  • the polymeric dispersant is useful to disperse particulate matter in a polar or non-polar organic media.
  • the particulate solid present in the composition may be any inorganic or organic solid material which is substantially insoluble in the organic medium at the temperature concerned and which it is desired to stabilize in a finely divided form therein.
  • the particulate solids may be in the form of a granular material, a fiber, a platelet or in the form of a powder, often a blown powder.
  • the particulate solid is a pigment.
  • the particulate solid (typically a pigment or filler) may have an average particle size measured by light scattering measurements of from 10 nanometers to 10 microns, or desirably 10 nanometers to 1, 2, 3 or 5 microns, or more desirably 20 nanometers to 1, 2, 3 or 5 microns in diameter.
  • suitable solids are pigments for solvent inks; pigments, extenders, fillers, blowing agents and flame retardants for paints and plastic materials; dyes, especially disperse dyes; optical brightening agents and textile auxiliaries for solvent dyebaths; pigments for inks, toners and other solvent application systems; solids for oil-based and inverse-emulsion drilling muds; dirt and solid particles in dry cleaning fluids; metals; particulate ceramic materials and magnetic materials for ceramics, piezoceramic printing, refractories, abrasives, foundry, capacitors, fuel cells, ferrofluids, conductive inks, magnetic recording media, water treatment and hydrocarbon soil remediation; organic and inorganic nanodisperse solids; metal, metal oxides and carbon for electrodes in batteries, fibers such as wood, paper, glass, steel, carbon and boron for composite materials; and biocides, agrochemicals and pharmaceuticals which are applied as dispersions in organic media.
  • the solid is an organic pigment from any of the recognized classes of pigments described, for example, in the Third Edition of the Colour Index (1971) and subsequent revisions of, and supplements thereto, under the chapter headed “Pigments.”
  • organic pigments are those from the azo, disazo, trisazo, condensed azo, azo lakes, naphthol pigments, anthanthrone, anthrapyrimidine, anthraquinone, benzimidazolone, carbazole, diketopyrrolopyrrole, flavanthrone, indigoid pigments, indanthrone, isodibenzanthrone, isoindanthrone, isoindolinone, isoindoline, isoviolanthrone, metal complex pigments, oxazine, perylene, perinone, pyranthrone, pyrazoloquinazolone, quinacridone, quinophthalone, thioindigo, triarylcarbonium
  • the organic pigments are phthalocyanines, especially copper phthalocyanines, monoazos, disazos, indanthrones, anthranthrones, quinacridones, diketopyrrolopyrroles, perylenes and carbon blacks.
  • inorganic pigments include metallic oxides such as titanium dioxide, rutile titanium dioxide and surface coated titanium dioxide, titanium oxides of different colours such as yellow and black, iron oxides of different colours such as yellow, red, brown and black, zinc oxide, zirconium oxides, aluminium oxide, oxymetallic compounds such as bismuth vanadate, cobalt aluminate, cobalt stannate, cobalt zincate, zinc chromate and mixed metal oxides of two or more of manganese, nickel, titanium, chromium, antimony, magnesium, cobalt, iron or aluminium, Prussian blue, vermillion, ultramarine, zinc phosphate, zinc sulphide, molybdates and chromates of calcium and zinc, metal effect pigments such as aluminium flake, copper, and copper/zinc alloy, pearlescent flake such as lead carbonate and bismuth oxychloride.
  • metallic oxides such as titanium dioxide, rutile titanium dioxide and surface coated titanium dioxide, titanium oxides of different colours such as yellow and black
  • Inorganic solids include extenders and fillers such as ground and precipitated calcium carbonate, calcium sulphate, calcium oxide, calcium oxalate, calcium phosphate, calcium phosphonate, barium sulphate, barium carbonate, magnesium oxide, magnesium hydroxide, natural magnesium hydroxide or brucite, precipitated magnesium hydroxide, magnesium carbonate, dolomite, aluminium trihydroxide, aluminium hydroperoxide or boehmite, calcium and magnesium silicates, aluminosilicates including nanoclays, kaolin, montmorillonites including bentonites, hectorites and saponites, ball clays including natural, synthetic and expandable, mica, talc including muscovites, phlogopites, lepidolites and chlorites, chalk, synthetic and precipitated silica, fumed silica, metal fibers and powders, zinc, aluminium, glass fibers, refractory fibers, carbon black including single and multi-walled carbon nanotubes, reinforcing and non-re
  • Other useful solid materials include flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate, melamine, melamine cyanurate, antimony oxide and borates; biocides or industrial microbial agents such as those mentioned in tables 2, 3, 4, 5, 6, 7, 8 and 9 of the chapter entitled “Industrial Microbial Agents” in Kirk-Othmer's Encyclopedia of Chemical Technology, Vol. 13, 1981, 3 rd Ed., and agrochemicals such as the fungicides flutriafen, carbendazim, chlorothalonil and mancozeb.
  • flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate,
  • the continuous medium in this disclosure can be a polar organic solvent, a non-polar organic solvent, or a polymer or compatible blends of polymers and/or solvents (wherein compatible is used to indicate a one-phase system under the intended conditions of temperature, pressure, etc.).
  • the organic medium present in the composition of the invention in one embodiment is a plastics material and in another embodiment is an organic liquid.
  • the organic liquid may be a non-polar or a polar organic liquid.
  • polar in relation to the organic liquid, it is meant that an organic liquid is capable of forming moderate to strong bonds as described in the article entitled “A Three-Dimensional Approach to Solubility” by Crowley, et al in Journal of Paint Technology, Vol. 38, 1966, at pg. 269.
  • Such organic liquids generally have a hydrogen bonding number of 5 or more as defined in the above-mentioned article.
  • Suitable polar organic liquids are amines, ethers, especially lower alkyl ethers, organic acids, esters, ketones, glycols, glycol ethers, glycol esters, alcohols and amides. Numerous specific examples of such moderately strongly hydrogen bonding liquids are given in the book entitled “Compatibility and Solubility” by Ibert Mellan (published in 1968 by Noyes Development Corporation) in Table 2.14 on pages 39-40 and these liquids all fall within the scope of the term polar organic liquid as used herein.
  • polar organic liquids are dialkyl ketones, alkyl esters of alkane carboxylic acids and alkanols, especially such liquids containing up to, and including, a total of 6 carbon atoms.
  • the polar organic liquids include dialkyl and cycloalkyl ketones, such as acetone, methyl ethyl ketone, diethyl ketone, di-isopropyl ketone, methyl isobutyl ketone, di-isobutyl ketone, methyl isoamyl ketone, methyl n-amyl ketone and cyclohexanone; alkyl esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, methyl propionate, methoxypropyl acetate and ethyl butyrate; glycols and glycol esters and ethers, such
  • solvents are alkanols, alkane carboxylic acids and esters of alkane carboxylic acids.
  • the present invention is suitable for organic liquids that are substantially non-soluble in an aqueous medium.
  • an aqueous medium such as glycols, glycol ethers, glycol esters and alcohols
  • small quantities of an aqueous medium such as glycols, glycol ethers, glycol esters and alcohols
  • an aqueous medium such as glycols, glycol ethers, glycol esters and alcohols
  • organic liquids which may be used as polar organic liquids are thermoplastic extrudable or moldable plastics and film-forming resins such as are suitable for the preparation of inks, paints and chips for use in various applications such as paints and inks.
  • resins include polyamides, such as VersamidTM and WolfamidTM, and cellulose ethers, such as ethyl cellulose and ethyl hydroxyethyl cellulose, nitrocellulose and cellulose acetate butyrate resins, including mixtures thereof.
  • paint resins include short oil alkyd/melamine-formaldehyde, polyester/melamine-formaldehyde, thermosetting acrylic/melamine-formaldehyde, long oil alkyd, medium oil alkyd, short oil alkyd, polyether polyols and multi-media resins such as acrylic and urea/aldehyde.
  • the organic liquid may be a polyol, that is to say, an organic liquid with two or more hydroxy groups.
  • polyols include alpha-omega diols or alpha-omega diol ethoxylates.
  • non-polar organic liquids are compounds containing aliphatic groups, aromatic groups or mixtures thereof.
  • the non-polar organic liquids include non-halogenated aromatic hydrocarbons (e.g., toluene and xylene), halogenated aromatic hydrocarbons (e.g., chlorobenzene, dichlorobenzene, chlorotoluene), non-halogenated aliphatic hydrocarbons (e.g., linear and branched aliphatic hydrocarbons containing six or more carbon atoms both fully and partially saturated), halogenated aliphatic hydrocarbons (e.g., dichloromethane, carbon tetrachloride, chloroform, trichloroethane) and natural non-polar organics (e.g., vegetable oil, sunflower oil, rapeseed oil, linseed oil, terpenes and glycerides).
  • non-polar organic liquids include non-halogenated aromatic hydrocarbons (e.g., to
  • the organic liquid comprises at least 0.1% by weight, or 1% by weight or more of a polar organic liquid based on the total organic liquid.
  • the organic liquid optionally further comprises water in amounts 10 wt. % or less, 5 wt. % or less or 2 wt. % or less in a polar organic media and water in amounts of 5 wt. % or less, 2 wt. % or less, or 1 wt. % or less in non-polar organic media based on the weight of the media.
  • the continuous media is substantially free of water meaning it is less than 500 ppm, 200 ppm or 100 ppm based on the weight of the media.
  • % or ppm of water will be based on the weight of the dispersion, which generally describes the millbase, coating or ink and comprises dispersed particulate, dispersant, and the polar or non-polar media, and optional additives such as resins, viscosity modifiers, defoamers, etc.
  • compositions of the present invention may contain other ingredients, for example resins (where these do not already constitute the organic medium), binders, co-solvents, cross-linking agents, fluidising agents, wetting agents, anti-sedimentation agents, plasticisers, surfactants, dispersants other than the compound of the present invention, humectants, anti-foamers, anti-cratering agents, rheology modifiers, heat stabilizers, light stabilizers, UV absorbers, antioxidants, leveling agents, gloss modifiers, biocides and preservatives.
  • resins where these do not already constitute the organic medium
  • binders for example resins (where these do not already constitute the organic medium), binders, co-solvents, cross-linking agents, fluidising agents, wetting agents, anti-sedimentation agents, plasticisers, surfactants, dispersants other than the compound of the present invention, humectants, anti-foamers, anti-cratering agents, rheology modifiers, heat
  • compositions containing plastic material may contain other ingredients, for example dispersants other than the compound of the present invention, antifogging agents, nucleators, blowing agents, flame retardants, process aids, surfactants, plasticisers, heat stabilizers, UV absorbers, anti-oxidants, fragrances, mould release aids, anti-static agents, anti-microbial agents, biocides, coupling agents, lubricants (external and internal), impact modifiers, slip agents, air release agents and viscosity depressants.
  • dispersants other than the compound of the present invention for example dispersants other than the compound of the present invention, antifogging agents, nucleators, blowing agents, flame retardants, process aids, surfactants, plasticisers, heat stabilizers, UV absorbers, anti-oxidants, fragrances, mould release aids, anti-static agents, anti-microbial agents, biocides, coupling agents, lubricants (external and internal), impact modifiers, slip agents, air release agents and viscosity depress
  • compositions typically contain from 1 to 95% by weight of the particulate solid (dispersed phase), the precise quantity depending on the nature of the solid and the quantity depending on the nature of the solid and the relative densities of the continuous media.
  • a composition in which the solid is an organic material, such as an organic pigment in one embodiment contains from 15 to 60% by weight of the solid whereas a composition in which the solid is an inorganic material, such as an inorganic pigment, filler or extender, in one embodiment contains from 40 to 90% by weight of the solid based on the total weight of composition.
  • compositions containing an organic liquid may be prepared by any of the conventional methods known for preparing dispersions.
  • the solid, the organic medium and the dispersant may be mixed in any order, the mixture then being subjected to a mechanical treatment to reduce the particles of the solid to an appropriate size, for example by high speed mixing, ball milling, basket milling, bead milling, gravel milling, sand grinding, attritor grinding, two or three roll milling, plastic milling until the dispersion is formed.
  • the solid may be treated to reduce its particle size independently or in admixture with either the organic medium or the dispersant, the other ingredient or ingredients then being added and the mixture being agitated to provide the composition.
  • the composition can also be made by grinding or milling the dry solid with the dispersant and then adding the liquid medium or mixing the solid with the dispersant in a liquid medium in a pigment flushing process.
  • the composition containing the plastic material may be prepared by any of the conventional methods known for preparing thermoplastic compounds.
  • the solid, the thermoplastic polymer, and the dispersant may be mixed in any order, the mixture then being subjected to a mechanical treatment to reduce the particles of the solid or disperse them in an appropriate size, for example, by Banbury mixing, ribbon blending, twin-screw extrusion, twin-roll milling, compounding in a Buss co-kneader, or similar equipment.
  • Master batches of the pigments in the particular plastic or rubber can also be made and that master batch can then be diluted with addition plastic or rubber to make the final composition.
  • composition of the present invention is particularly suited to liquid dispersions.
  • such dispersion compositions comprise:
  • component a) comprises from 0.5 to 30 parts of a pigment and such dispersions are useful as (liquid) inks, paints and millbases.
  • the organic liquid is typically volatile so that it may be readily removed from the particulate solid by a simple separation means such as evaporation.
  • the composition comprises the organic liquid.
  • the dry composition consists essentially of the polymeric dispersant and the particulate solid, it typically contains at least 0.2%, at least 0.5% or at least 1.0% of polymeric dispersant based on weight of the particulate solid. In one embodiment, the dry composition contains not greater than 100%, not greater than 50%, not greater than 20% or not greater than 10% by weight of the polymeric dispersants based on the weight of the particulate solid.
  • compositions of the invention are suitable for preparing millbases wherein the particulate solid is milled in an organic liquid in the presence of said polymeric dispersant.
  • a millbase comprising a particulate solid, an organic liquid and the polymeric dispersant.
  • the millbase contains from 20 to 70% by weight particulate solid based on the total weight of the millbase. In one embodiment, the particulate solid is not less than 10 or not less than 20% by weight of the millbase. Such millbases may optionally contain a binder added either before or after milling.
  • the binder is a polymeric material capable of binding the composition on volatilization of the organic liquid.
  • Binders are polymeric materials including natural and synthetic materials.
  • binders include poly(meth)acrylates, polystyrenics, polyesters, polyurethanes, alkyds, polysaccharides such as cellulose, nitrocellulose, and natural proteins such as casein.
  • the binder may be nitrocellulose. In one embodiment, the binder is present in the composition at more than 100% based on the amount of particulate solid, more than 200%, more than 300% or more than 400%.
  • the amount of optional binder in the millbase can vary over wide limits but is typically not less than 10%, and often not less than 20% by weight of the continuous/liquid phase of the millbase. In one embodiment, the amount of binder is not greater than 50% or not greater than 40% by weight of the continuous/liquid phase of the millbase.
  • the amount of dispersant in the millbase is dependent on the amount of particulate solid but is typically from 0.5 to 5% by weight of the millbase.
  • Dispersions and millbases made from the composition of the invention are particularly suitable for use in non-aqueous and solvent free formulations in which energy curable systems (ultra-violet, laser light, infra-red, cationic, electron beam, microwave) are employed with monomers, oligomers, etc. or a combination present in the formulation. They are particularly suitable for use in coatings such as paints, varnishes, inks, other coating materials and plastics.
  • energy curable systems ultra-violet, laser light, infra-red, cationic, electron beam, microwave
  • Suitable examples include their use in low, medium and high solids paints, general industrial paints including baking, two component and metal coating paints such as coil and can coatings, powder coatings, UV-curable coatings, wood varnishes; inks, such as flexographic, gravure, offset, lithographic, letterpress or relief, screen printing and printing inks for packaging printing, non-impact inks such as inkjet inks including continuous inkjet and drop on demand inkjet which include thermal, piezo and electrostatic, phase change inks and hot melt wax inks, inks for ink-jet printers and print varnishes such as overprint varnishes; polyol and plastisol dispersions; non-aqueous ceramic processes, especially tape-casting, gel-casting, doctor-blade, extrusion and injection moulding type processes, a further example would be in the preparation of dry ceramic powders for isostatic pressing; composites such as sheet moulding and bulk moulding compounds, resin transfer moulding, pultrusion, hand-
  • composition of the invention further includes one or more additional known dispersants.
  • the polymeric dispersant of the invention herein is useful for making various particulate dispersions that go into inks, coatings, LCD (liquid crystal display) panels, and pigmented or filled polymer systems.
  • a liquid-crystal display is a flat-panel display or other electronically modulated optical device that uses the light-modulating properties of liquid crystals.
  • the color filter composition is for a Quantum dot color filter.
  • the novel copolymers are especially useful in color filter application.
  • the color filter composition is comprising a) photo resist binder, b) transparent pigment, c) optionally a solvent and/or optionally a photoinitiator or a photolatent catalyst, and d) dispersant which is block copolymer of any of the appended composition or process claims.
  • photo resist binder refers to a photosensitive resin which is preferably an acid-curable resin or a photo curable resin such as acrylate, photo curable acrylate oligomer, polyester, alkyd, melamine, urea, epoxy and phenolic resins or mixtures thereof.
  • Acid-curable resins of that kind are generally known and are described, for example, in “Uilmann's Encyclopdie der ischen Chemie,” Edition 4, Vol. 15 (1978), pp. 613-628. Preferred are (meth)acrylate/(meth)acrylic acid copolymers.
  • copolymers are copolymers of methyl (meth)acrylate and (meth)-acrylic acid, copolymers of benzyl (meth)acrylate and (meth)acrylic acid, copolymers of methyl (meth)acrylate/, ethyl (meth)acrylate and (meth)acrylic acid, copolymers of benzyl (meth)acrylate, (meth)acrylic acid and styrene, copolymers of benzyl (meth)acrylate, (meth)acrylic acid and 2-hydroxyethyl (meth)acrylate, copolymers of methyl (meth)acrylate/, butyl (meth)acrylate, (meth)acrylic acid and styrene, copolymers of methyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid and hydroxyphenyl (meth)acrylate, copolymers of methyl (meth)acrylate,
  • a photo curable acrylate oligomer is preferably present in addition to the photo curable resin.
  • Photo curable acrylate oligomers usable herein include dipentaerythritol hexaacryl (DPHA), dipentaerythritol pentaacrylate (DPPA), pentaerythritol triacrylate (PETTA), trimethylol-propane triacrylate (TMPTA), and trimethylolpropane triacrylate (TMPTA) and the like.
  • the term transparent pigment refers to a pigment which gives a transparently colored ink when dispersed.
  • the pigment may be inorganic or preferably organic, for example carbon black or pigments of the 1-aminoanthraquinone, anthanthrone, anthrapyrimidine, azo, azomethine, quinacridone, quinacridonequinone, quinophthalone, dioxazine, diketopyrrolopyrrole, flavanthrone, indanthrone, isoindoline, isoindolinone, isoviolanthrone, perinone, perylene, phthalocyanine, pyranthrone or thioindigo series, including those, where applicable, in the form of metal complexes or lakes, in particular unsubstituted or partially halogenated phthalocyanines such as copper, zinc or nickel phthalocyanines, 1,4-diketo-3,6-diaryl-pyrrolo[3,4-c]pyrrol
  • CE1 is a comb type copolymer with a styrene maleic anhydride back bone and pendant polyether chains.
  • the synthesis is based on Example 10 from WO2008/122606A except propylene glycol monomethyl ether acetate replaces ethyl acetate
  • Styrene maleic anhydride copolymer (ex: Cray Valley, 3000 Mn, 12.5 parts by weight) and propylene glycol monomethyl ether acetate (80 parts) were stirred under nitrogen at 25° C. for 3 hours.
  • Surfonamine B200 (ex Huntsman, 40.75 parts) was added over a period of 35 minutes. The reaction was stirred at 25° C. for 18 hours. The reaction mixture was then heated to 60° C. for 3 hours. A sample (61.6 parts) was removed at this stage.
  • n-Butyl methacrylate (490 parts), butyl-2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl] propionate (CTA-1 ex Lubrizol, 118.62 parts) and propylene glycol monomethyl ether acetate (792.10 parts) were stirred under nitrogen at 80° C.
  • 2,2′-Azobis(2-methylpropionitrile) (2.32 parts) propylene glycol monomethyl ether acetate (20 parts) were charged over 2 hours at 80° C.
  • reaction mixture was heated at 80° C. for 10 hours until the monomer conversion reached 100%.
  • n-Butyl acrylate (320 parts), butyl-2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propionate (CTA-1 ex Lubrizol, 13 parts), 2,2′-azobis(2-methylpropionitrile) (0.256 parts) and propylene glycol monomethyl ether acetate (474 parts) were stirred at 70° C. under nitrogen for 5 hours. 2,2′-azobis(2-methylpropionitrile) (0.256 parts) was added and the reaction stirred at 70° C. for 6.5 hours until monomer conversion had exceeded 90% as determined by solids content.
  • Examples 1-4 (1 part based on 100% active material) was dissolved in propylene glycol monomethyl ether acetate (8 parts). Glass beads (17 parts, 1 mm diameter) and red pigment (1 part, Irgaphor® Red S3621, ex BASF) were added and the contents were milled on a horizontal shaker for 48 hours. The resultant millbase was a fluid dispersion with the exception of Comparative Examples 1 and 2, which both gelled.
  • PSD particle size of the mill base was evaluated by diluting the dispersions (0.1 parts) with propylene glycol monomethyl ether acetate (20 parts) and evaluated using a Nanotrac particle size analyser.
  • the millbases were then heated in an oven at 40-45° C. for 96 hours and the particle size (PS) of the mill base was evaluated by diluting the dispersions (0.1 parts) with propylene glycol monomethyl ether acetate (20 parts) and evaluated using a Nanotrac particle size analyzer.
  • PSD particle size of the mill base was evaluated by diluting the dispersions (0.1 parts) with propylene glycol monomethyl ether acetate (20 parts) and evaluated using a Nanotrac particle size analyzer.
  • the millbases remained stable by particle size with the exception of CE1.
  • the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of” and “consisting of,” where “consisting of” excludes any element or step not specified and “consisting essentially of” permits the inclusion of additional unrecited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
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  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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CN111273499A (zh) * 2020-03-27 2020-06-12 深圳秋田微电子股份有限公司 一种具有稳态的电泳显示液及其制备方法
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CN112852213A (zh) * 2021-01-13 2021-05-28 安徽博纳新材料科技有限公司 一种超枝化水性分散剂的制备方法
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